Methylalkoxy-methylalkyl cyclosiloxane copolymer

ABSTRACT

A methylalkoxy-methylalkyl cyclosiloxane copolymer having the formula 
     
         (OSiROR).sub.d (OSiRR&#39;).sub.e 
    
     where R is an alkyl radical having one to three carbon atoms; R&#39; is the alkyl radical (CH 2 ) c  R; c is an integer having a value of from 1 to 17; d is an integer having a value of from 3 to 10; and e is an integer having a value of from one to seven.

This is a division of copending application Ser. No. 578,715, filed9/7/90.

BACKGROUND OF THE INVENTION

This invention relates to siloxane and siloxane copolymer masonry waterrepellent compositions, and more particularly is directed to a waterrepellent composition for treating porous substrates which is anemulsion including a copolymer such as a linearmethylhydrogenmethylalkyl siloxane or a methylhydrogen-methylalkylcyclosiloxane.

Water resistance is an important factor in concrete and masonryconstruction. This is for the reason that moisture movement in concretecauses or contributes to problems such as expansion, shrinkage,cracking, staining, mildew, lowered resistance to freezing and thawing,chemical attack, corrosion of reinforcing steel, and damage tostructures from settling. Because of these problems, various techniqueshave been used to render concrete water resistant. Some of these methodsinclude the surface treatment of concrete structures with waterrepellents. Water repellents that have been used in the past are oils,waxes, soaps, resins and organosilicon compounds, and they have beenapplied to the masonry surfaces by brush, roller, air spray, or airlessspray techniques. One of the most prevalent category of repellent thathas been used is organosilicon compounds, and such compounds in organicsolvents have been found to be useful for brick, concrete, stucco, orterrazo surfaces.

It is not new in the art to employ organosilicon compounds for thetreatment of masonry surfaces in order to render such surfaces waterrepellent. For example, in U.S. Pat. No. 3,772,065, issued Nov. 13,1973, there is disclosed an impregnant which is an alcohol orhydrocarbon solution of alkyltrialkoxysilanes or oligomers thereof. InU.S. Pat. No. 3,849,357, issued Nov. 19, 1974, a composition isdescribed which is a mixture of a water base paint, and the reactionproduct of an alkyltrialkoxysilane, an alkyl orthosilicate, and water.U.S. Pat. Nos. 3,389,206, issued Apr. 22, 1975, and 4,002,800, issuedJan. 11, 1977, there is disclosed a solution containing an alcohol orhydrocarbon solvent, an alkyltrialkoxysilane, and an additive. Theadditive is either an organofunctional silane such asaminopropyltriethoxysilane or an alcoholate such as butyl titanate. U.S.Pat. No. 3,914,476, issued Oct. 21, 1975, refers to an aqueous solutioncontaining an alkali metal organosiliconate, and an aqueous solublecarbonate or bicarbonate. In U.S. Pat. No. 3,955,985, issued May 11,1976, an aqueous solution is described containing an alkali metalorganosiliconate, a miscible alcohol or ketone, and an organiccomplexing or chelating agent such as nitrilotriacetic acid.

U.S. Pat. No. 3,956,570, issued May 11, 1976, applies an aqueoussolution of an alkali metal propysiliconate. Surfaces are contacted withwater followed by treatment with a mixture of calcium hydroxide andbutyltrimethoxysilane in ethyl alcohol in U.S. Pat. No. 4,073,972,issued Feb. 14, 1978. In U.S. Pat. No. 4,076,868, issued Feb. 28, 1978,there is applied a solvent solution thickened with a filler, andcontaining either (i) a polysiloxane having a viscosity less than 1000cs, (ii) an alkyltrialkoxysilane, or (iii) an alkali metal hydrocarbonsiliconate. U.S. Pat. No. 4,102,703, issued July 25, 1978, forms astable suspension of hydrophobed metal oxides in ethylene glycol, andapplies the suspension to masonry. Hydrophobing is accomplished witheither (i) organohalosilanes, (ii) organosilylamines, (iii) cyclicorganosilazanes, (iv) organocyclosiloxanes, (v) polyorganosiloxanes,(vi) alkylhydrogen silicone oils, or (vii) hydroxy endblockedpolyorganosiloxanes.

In U.S. Pat. No. 4,209,432, issued June 24, 1980, the patentee applies asolvent solution containing a filler such as fume silica, and containingeither (i) an organosiloxane having more than ten silicon atoms permolecule, (ii) an alkyltrialkoxysilane, (iii) the reaction product of asilane and ethylene glycol, or (iv) an alkali metal hydrocarbonsiliconate. U.S. Pat. No. 4,273,813, issued June 16, 1981, employs acoating of an emulsion of an anionically stabilized hydroxy endblockedpolydiorganosiloxane, amorphous silica, and an organic tin salt. In U.S.Pat. No. 4,342,796, issued Aug. 3, 1982, the patentee dries the surfaceto be treated, applies an alkyltrialkoxysilane to the dried surface,allows the silane to migrate into the surface, and applies water to thetreated surface. U.S. Pat. No. 4,352,894, issued Oct. 5, 1982, appliesan aqueous solution of an alkylsilanol prepared frompropyltrimethoxysilane. A coating of a moisture curable urethane resinand an alkylpolysiloxane or hydroxyalkyl polysiloxane such as2-ethyl-hexyl polysiloxane, stearyl polysiloxane, or hydroxyethylpolysiloxane, is disclosed in U.S. Pat. No. 4,413,102, issued Nov. 1,1982. In U.S. Pat. No. 4,433,013, issued Feb. 21, 1984, there is appliedan emulsion of an akyltrialkoxysilane including a deactivatablesurfactant such as a fatty acid ester or silica ester. After theemulsion is applied, the surfactant is deactivated with water containingan alkaline or acid substance. U.S. Pat. No. 4,478,911, issued Oct. 23,1984, relates to a coating which includes an alkyltrialkoxysilane,water, an organic solvent, and a catalyst such as an organic amine. InU.S. Pat. No. 4,486,476, issued Dec. 4, 1984, the patentee impregnateswith a water immiscible solvent such as naphtha containing a mixture ofa methyl-ethoxysiloxane having an ethoxy content of 12 percent and amethyl-ethoxysiloxane having an ethoxy content of 43 percent.

U.S. Pat. No. 4,631,207, issued Dec. 23, 1986, employs a solvent such asa glycol ether containing the reaction product ofoctamethylcyclotetrasiloxane and N-(2-aminoethyl)-3-aminopropyldimethoxy-methylsilane. Reexamined U.S. Pat. No. B1 4,648,904, issuedMar. 10, 1987, is directed to an emulsion of an alkyltrialkoxysilane, anemulsifier having an HLB value of 2-20, and water. A solution containingan alkylalkoxy polysiloxane resin is applied to masonry in U.S. Pat. No.4,717,599, issued Jan. 5, 1988. An oily composition or emulsion isdisclosed in U.S. Pat. No. 4,741,773, issued May 3, 1988, containing amixture of a silicone oil with either a nonvolatile paraffinic oil suchas turbine oil or a nonvolatile low molecular weight hydrocarbon resinsuch as polybutene. In U.S. Pat. No. 4,753,977, issued June 28, 1988,the treating composition includes an organopolysiloxane resin, analkylalkoxy polysiloxane resin, and a condensation catalyst. A sealerincluding a hydroxy-substituted polyorganosiloxane and a mixturecontaining (i) an aromatic solvent such as toluene, (ii) a chlorinatedsolvent such as trichloroethane, and (iii) an aliphatic solvent such asheptane, is taught in U.S. Pat. No. 4,786,531, issued Nov. 22, 1981.

In U.S. Pat. No. 4,846,886, issued July 11, 1989, and in U.S. Pat. No.4,874,431, issued Oct. 17, 1989, the patentees apply a combination of(i) a carrier such as an alcohol, glycol ether, or mineral spirits, (ii)a metal salt catalyst, (iii) an alkylalkoxysilane, and (iv) a beadingagent such as a fluorosilicone fluid, a polydimethylsiloxane fluid, aroom temperature curable silicone rubber, an amine salt functionalsiloxane copolymer, or trimethylsilyl endcapped polysilicate. A bufferedaqueous silane emulsion is disclosed in U.S. Pat. No. 4,877,654, issuedOct. 31, 1989, and U.S. Pat. No. 4,889,747, issued Dec. 26, 1989,containing a hydrolyzable silane, an emulsifier with an HLB value of1.5-20, water, and a buffering agent.

As noted, it is not new to treat masonry surfaces with organosiliconcompounds for the purpose of rendering the masonry water repellent. Onecategory of organosilicon compound which has been used extensively isthe alkoxysilane, and representative of such masonry treatments withalkoxysilanes can be found in U.S. Pat. No. 3,772,065, issued Nov. 13,1973; U.S. Pat. No. 3,879,206, issued Apr. 22, 1975; U.S. Pat. No.4,478,911, issued Oct. 23, 1984; U.S. Pat. No. 4,648,904, issued Mar.10, 1987; U.S. Pat. No. 4,846,886, issued July 11, 1989; and U.S. Pat.No. 4,874,431, issued Oct. 17, 1989. Another category of organosiliconcompound frequently used in masonry treatment is the siloxane.Representative of such masonry treatments with siloxanes can be found inU.S. Pat. No. 4,209,432, issued June 24, 1980; U.S. Pat. No. 4,342,796,issued Aug. 3, 1982; and U.S. Pat. No. 4,753,977, issued June 28, 1988.The present invention includes siloxanes in one embodiment and thesiloxanes of that embodiment differ from the siloxane compositions ofthe prior art in the presence in the siloxane molecule of the silylidyneradical ##STR1## This difference is significant as will be pointed outhereinafter.

SUMMARY OF THE INVENTION

This invention is directed to a water repellent composition for treatingporous substrates with an aqueous emulsion containing a siloxane orsiloxane copolymer. The siloxane may be either a linear methylhydrogensiloxane or a cyclic methylhydrogen siloxane. The siloxane copolymer iseither a linear methylhydrogen-methylalkyl siloxane copolymer or amethylhydrogen-methylalkyl cyclosiloxane copolymer.

The invention is also directed to a method of producing on a poroussubstrate a water shedding surface coating by applying to the poroussubstrate a composition in the form of an emulsion formed by combining asiloxane with a surfactant and water for producing on the surface of theporous substrate a durable water shedding surface coating.

It is therefore an object of the present invention to chemically fix awater-repelling agent to a porous substrate such as concrete, limestone,and natural stone, in order to improve its resistance to the absorptionof water as well as to impart to the surface thereof the ability to shedsurface water.

It is a further object of the present invention to increase the densityof a silicone matrix within a porous substrate such as concrete,limestone, and stone, in order to render the substrate water resistant,and at the same time provide it with the property of shedding surfacewaters.

It is also an object of the present invention to provide a penetratingmasonry water repellent composition for porous substrates such asconcrete and limestone as well as other non-reactive masonry surfaces inwhich the repellent not only renders the substrate resistant to waterpenetration but in addition hinders the ingress of water at the surface.

These and other objects, features, and advantages of the hereindescribed invention will become more apparent from a consideration ofthe following detailed description thereof.

DETAILED DESCRIPTION OF THE INVENTION

Masonry water repellents including alkylalkoxysilanes impart waterrepellent properties to such porous substrates as concrete, mortar, andstone. Such repellents function in this fashion because of the fact thatthey penetrate into the masonry prior to the time that they aretransformed into immobile resinous materials. However, due to thepenetration of the repellent into the porous substrate, the repellentdoes not leave behind much of a layer on the porous substrate. As aresult, the repellent, though effective to render the substrate waterresistant fails nevertheless to provide the substrate with coatings ofany significant durability. The compositions disclosed herein areintended to overcome this deficiency and there can be achieved a gooddegree of water shedding function of the masonry structure because ofpolymer deposition on the surface of the masonry, in addition to thepenetration of the repellent formulation to provide a deep section waterbarrier to water migration within the substrate itself.

The penetrating masonry water repellents of the present invention haveparticular application to the highway industry where water resistance isrequired for bridge decks, roads, and parking garages. In addition, suchcompositions are applicable especially to the building industry whichmakes use of masonry materials for walls such as natural stones whichare porous and contain neutral mineral components including, forexample, limestone, marble, and granite. These heretofore difficult totreat building materials can be effectively rendered water resistantwith the compositions of the present invention. While the highwayindustry applications of the formulations will be primarily concrete,the building industry applications of the formulations can range frombrick, natural stone, as noted above, cinder block, and stucco.

Generally, concrete, brick, and stucco, may be treated with analkylalkoxysilane rendering the substrate water resistant. The latentalkalinity of such substrates promotes the hydrolysis and condensationof the silane into a resinous silicone matrix being permanently formedand deposited within the interior of the concrete, brick, or stuccosubstrate. Natural stone, such as limestone, is an exception in that itis relatively neutral and possesses no latent catalytic activity. As aconsequence, the silane will not convert to a silicone as rapidly, norwill it affix itself to the calcareous interior surfaces of thesubstrate. The result is that there is provided very little or no waterrepellency or resistance to water absorption. This lack of reactivity oflimestone is particularly noticeable when limestone aggregate isemployed as a constituent in the preparation of concrete. In suchinstance, water readily penetrates along the interfacial boundariesbetween the concrete and the course limestone aggregate. Since thesilane-based repellent does not adhere to the limestone, those portionsof the concrete adjacent the aggregate are not rendered water resistantwhereas the remainder of the concrete substrate is treated successfully.The water takes the path of least resistance into the mass of concrete,therefore, migrating along the side or through the aggregate oflimestone particles. It is for these types of situations that certainembodiments of the present invention are particularly useful along withtheir capacity to shed water at the surface of the substrate.

The masonry water repellent compositions of the present inventionincluding their capability of water shedding have wide applicationincluding for example, concrete products such as precast products,blocks, brick, pipe, prestressed products, structural concrete, andhighway surfacing; floor and wall tiles, roofing tile, and structuraltiles; in Portland cement concrete work containing coarse limestoneaggregate as footings, poured foundations, paving, steps, curbs,structural products, molded, reinforced, and prestressed concreteproducts such as blocks, bricks, pipes, panels, and beams; exterior andinterior plaster; stucco; and terrazo.

A major advantage of the repellent compositions of the present inventionis that the compositions are capable of being formulated into a formwhich complies with various state and federal regulations regardingvolatile organic content (VOC). These regulations generally prohibit avolatile organic content for an architectural coating which is in excessof about four hundred grams per liter. In the case of the compositionsof the present invention, no volatile component is liberated from thereaction of the penetrant with concrete. Prior art solvent basedalkoxysilanes on the other hand, liberate alcohol which is a volatileorganic compound.

Accordingly, a penetrant can be formulated with the compositions of thepresent invention which complies with the volatile organic contentregulations. Thus, a penetrant in accordance with the present inventionwill have a volatile organic content generally less than about fourhundred grams per liter. In contrast, equivalent penetrants of the priorart which contain alkoxysilanes such as isobutyltrimethoxysilane havevolatile organic contents of the order of magnitude of about 650-700grams per liter.

The water repellent composition for treating porous substrates inaccordance with the present invention is an emulsion containing water,at least one surfactant, and a siloxane which is either a linearmethylhydrogen siloxane, a methylhydrogen-methylalkyl siloxanecopolymer, a methylhydrogen cyclosiloxane, or amethylhydrogen-methylalkyl cyclosiloxane copolymer. The siloxane has theformula selected from the group consisting of ##STR2## where R is analkyl radical having one to three carbon atoms; R' is the alkyl radical(CH₂)_(c) R; a is an integer having a value of from 3 to 35; b is aninteger having a value of from zero to 32; c is an integer having avalue of from one to seventeen; d is an integer having a value of from 3to 10; and e is an integer having a value of from zero to seven.Formulas I and II cover a first embodiment, whereas Formula III relatesto an alternate form of the invention.

The emulsion can include from about twenty to about sixty percent byweight of the siloxane, and preferably the emulsion includes forty tofifty percent by weight of the siloxane. Preferably, the integer a has avalue of three or four; the integer b has a value of two or three; theinteger c has a value of five, six, or seven; the integer d has a valueof three or four; and the integer e has a value of one or two.

The following examples are set forth for the purpose of illustrating thebasic concepts of the present invention including the method ofpreparing the siloxane copolymers of the present invention.

EXAMPLE I

In a 250 ml round bottom flask equipped with a reflux condenser and aheating mantle was placed a solution of 48 g of (OSiMeH)₄ and 16.8 g of1-hexene. One piece of 8 mesh 0.5% Pt/C of 40 mg total weight, or about0.2 mg Pt. was added to the solution and the contents of the flask wereheated to reflux. An exotherm occurred during heating for about 10minutes. The mixture was heated at reflux for an additional 15 minutes,after which it was allowed to cool to room temperature. FourierTransform Infrared Analysis of an alliquot of the mixture revealed thepresence of SiH and the absence of olefin. Gas chromatography/massspectrometry analysis revealed the product to be a mixture having thefollowing composition:

    ______________________________________                                        (OSiMeH).sub.4           15%                                                  (OSiMeH).sub.3 /(OSiMeC.sub.6 H.sub.13)                                                                50%                                                  (OSiMeH).sub.2 /(OSiMeC.sub.6 H.sub.13).sub.2                                                          25%                                                  (OSiMeH)/(OSiMeC.sub.6 H.sub.13).sub.3                                                                 10%                                                  ______________________________________                                    

EXAMPLE II

Following the same procedure of Example I, a mixture of 75 g of Me₃Si--(OSiMe₂)₃ (OSiMeH)₅ --OSiMe₃) and 18.4 g of 1-hexene was allowed toreact in the presence of 0.2 mg Pt as 0.5% Pt/C.

EXAMPLE III

A solution of 333 g of (OSiMeH)₄ and 210 g of 1-dodecene (C₁₂ H₂₄) wasprepared by weighing the two compounds into a 1 liter bottle andstirring the contents for 1 minute. 100 g of this solution was placedinto a 1 liter round bottom flask equipped with a reflux condenser and aheating mantle. Two pieces of 8 mesh 0.5% Pt on C (0.2 mg Pt each) wereadded to the flask and the mixture was heated to boiling. The remainderof the solution was poured into a 500 ml dropping funnel, which wasplaced near the top opening of the reflux condenser. When the mixture inthe flask started to boil, solution from the dropping funnel was addedslowly through the reflux condenser. The fresh solution was added to themixture at such a rate so as to maintain a gentle reflux in the flask.Addition of the solution in the dropping funnel required about 45minutes. After all of the solution had been added, the mixture in theflask was heated at reflux for an additional 15 minutes, after which itwas allowed to cool to room temperature and filtered throughdiatomaceous earth.

The reaction scheme for the process of preparing and using thecomposition of Example I can be seen as follows: ##STR3##

Thus, methylhydrogen cyclosiloxane is reacted with the olefin 1-hexenein the presence of a platinum-carbon catalyst to produce a low molecularweight siloxane penetrant having alkylmethylsiloxy and organohydrosiloxygroups. When applied to concrete, for example, the low molecular weightsiloxane penetrant having alkylmethylsiloxy and organohydrosiloxy groupsof the formula (OSiMeH)₀.75 (OSiMeC₆ H₁₃)₀.25 is converted by hydrolysisand subsequent condensation to a copolymeric silicone resin of theformula (MeSiO_(3/2))₀.75 (OSiMeC₆ H₁₃)₀.25. This resin is present onthe surface and in the pores of the concrete, and renders it resistantto water.

This hydrosilylation reaction of the olefin with a low molecular weightmethylhydrogen siloxane does not usually produce a pure compound, but amixture of compounds is produced, and this mixture is used as thewaterproofing penetrant. It is not necessary to use pure compounds aspenetrants, since upon application to concrete, the penetrant hydrolyzesand condenses to form a silicone resin.

As previously noted, the compositions of the first embodiment of thepresent invention differ from the siloxane compositions of the prior artin the presence in the siloxane molecule of the silylidyne radical##STR4## This difference is significant since the silylidyne radicalreacts with the hydroxide groups and moisture in the masonry substrateto form the copolymeric silicone resin described above. This resin isformed within the pores of the masonry substrate to which the repellentcomposition is applied. The copolymeric silicone resin that is formedwithin the masonry substrate pores is hydrophobic and therefore readilyresists the permeation of water onto and into the porous surface andinterior of the masonry material. The compositions of the firstembodiment of the present invention have a relatively low viscosity andtherefore are capable of diffusing and penetrating into porous masonrysubstrates to which they are applied. When applied to a masonrysubstrate such as concrete, for example, the latent alkalinity of theconcrete catalyzes the reactions of water and hydroxide groups with thesilylidyne radical to produce SiOH and hydrogen. The alkaline concretefurther catalyzes the condensation of SiOH groups to produce siloxanebonds and water, and a resinous structure is ultimately produced.

As noted above, the repellent compositions of the present invention arecapable of being formulated into coatings which comply with variousstate and federal regulations regarding volatile organic content (VOC).These regulations prohibit a volatile organic content architecturalcoating in excess of four hundred grams per liter. In the firstembodiment of the present invention, the volatile component liberatedfrom the reaction of the penetrant with concrete is hydrogen which isnot a volatile organic compound. In the alternate embodiment of thepresent invention, even the liberated hydrogen can be eliminated by thereplacement of SiH with alkoxy using an amine catalyst. Prior artalkoxysilanes on the other hand, liberate alcohol which is a volatileorganic compound.

Accordingly, a penetrant can be formulated with the compositions of thepresent invention which complies with the volatile organic contentregulations. Thus, a penetrant in accordance with the present inventioncontaining about forty-five to about fifty percent by weight solids willhave a volatile organic content less than about four hundred grams perliter. Penetrants of the prior art which contain alkoxysilanes such asisobutyltrimethoxysilane have volatile organic contents about 650-700grams per liter.

Although the alkyl group of the siloxanes described in the presentinvention contribute to the ability of the compound to render concretehydrophobic, its presence is not always required. Thus, methylhydrogensiloxane may be used to waterproof concrete, and the resulting siliconeresin formed after complete hydrolysis and condensation ismonmethylsilsequioxane or MeSiO3/2. This material is substantiallyhydrophobic and readily renders concrete hydrophobic. However, there areadvantages in using an alkylmethyl/methylhydrogen copolymeric materialin lieu of the methylhydrogen siloxane. Thus, the olefins used toprepare alkylmethylsiloxane/methylhydrogen copolymers are less expensivethan methylhydrogen siloxane from which these copolymeric materials areprepared. Hence material expense for alkylmethyl/methylhydrogencopolymeric compounds is less than methylhydrogen siloxane because theformer is essentially the latter diluted with olefin. Even though thecopolymeric materials require more processing than methylhydrogensiloxane, expense of the alkylmethylsiloxane/methylhydrogen copolymerare still lower than methylhydrogen siloxane. The copolymer also is lessvolatile and has a higher flash point than methylhydrogen siloxane.

The following additional examples illustrate details in the process forpreparing the low volatile organic content emulsion coating compositionsof the first embodiment of the instant invention.

The preferred starting material is a methylhydrogencyclosiloxane such as(OSiMeH)₄. However, mixtures of these cyclic siloxanes are as effectiveas the pure cyclic compound. The preferred olefin is 1-hexene. Otherolefins include 1-pentene, 1-heptene, 1-octene, 1-decene or 1-dodecene.Mixtures of these olefins can also be used to make the compositions. Theratio of SiH to olefin can be varied, but this ratio should be such thata minimum of three SiH groups per molecule is retained. For example, ifpure (OSiMeH)₄ is used, no more then one mole of olefin should be usedper mole of cyclosiloxane. The method of hydrosilylation uses aheterogenous catalyst such as 0.5 % Pt/C. A mixture of the SiH compound,olefin and catalyst is heated to reflux for approximately 30 minutes. Ifthe batch size is large, it is advisable to reflux a small portion ofthe mixture while adding the remainder in small increments to controlthe highly exothermic reaction. The product from this reaction, a lowviscosity oil, is a mixture of compounds having an average stoichiometryof (OSiMeH)₀.75 /(OSiMeR).sub. 0.25 wherein R=Me, C₆ H₁₃, or C₁₂ H₂₃.

The low viscosity oil is homogenized with water and a surfactant toproduce an oil in water nonionic emulsion having a solids content ofabout 30 percent by weight. As long as the pH of the emulsion is nearneutral, hydrolysis of SiH is insignificant. When applied to asubstrate, water evaporates to leave a low viscosity oil which diffusesand penetrates. When the substrate is alkaline, such as concrete, thisalkalinity will catalyze reactions of hydrolysis/condensation.Specifically, SiH reacts with moisture and hydroxyls present in thesubstrate to produce SiOH+H₂. SiOH condenses to produce siloxane+H₂ O.Since the silicone oil is multifunctional, a resinuous structure will beformed with complete hydrolysis/condensation. This resin, being highlyhydrophobic, waterproofs the substrate.

EXAMPLE IV

A solution of 300 g of (OSiMeH)₄ and 105 g of 1-hexene (C₁₂ H₂₄) wasprepared by weighing the two compounds into a one liter bottle andstirring the contents for one minute. 100 Grams of this solution wasplaced into a one liter round bottom flask equipped with a refluxcondenser and a heating mantle. Two pieces of eight mesh 0.5% Pt onCarbon (0.2 mg Pt each) were added to the flask and the mixture washeated to boiling. The remainder of the solution was poured into a 500ml dropping funnel which was placed near the upper opening of the refluxcondenser. When the mixture in the flask started to boil, solution fromthe dropping funnel was added slowly through the reflux condenser. Thefresh solution was added to the mixture at such a rate so as to maintaina gentle reflux in the flask. Addition of the solution in the droppingfunnel required about 30 minutes. After all of the solution had beenadded, the mixture in the flask was heated at reflux for an additional20 minutes, after which it was allowed to cool to room temperature andfiltered through diatomaceous earth. FTIR analysis revealed the presenceof SiH and the absence of olefin.

To 300 grams of this product was added 6 grams of the nonionicsurfactant TERGITOL® TMN-6 and 694 grams of distilled water. The mixturewas stirred for 30 minutes and homogenized using a Gaulin laboratoryhomogenizer to produce an oil in water emulsion having a solids contentof about 30 percent by weight. With the same procedure, (OSiMeH)₄ waspartially reacted with 1-dodecene using one mole of olefin to one moleof (OSiMeH)₄ and the product was homogenized to obtain a 30% solidsemulsion. (OSiMeH)₄ was also emulsified using the above procedure toproduce a 30% solids emulsion. 200 grams portions of the three emulsionswere diluted with water to produce emulsions having a solids content of15% by weight. The 15% solids emulsions and the 30% solids emulsionswere used to treat 3"×5"×1" concrete blocks, and the block were testedfor water repellency according to the method described in the NationalCooperative Highway Research Program Report 244, Transportation ResearchBoard, December, 1981, D.W. Pfeiffer & M.J. Scali; Wiss, Janney, Elstner& Associates. The test results are shown in Tables I and II.

While a nonionic surfactant is shown in Example IV, other types ofsurfactants can be employed in accordance with the present invention.Thus, the emulsions of the present invention can be formulated withnonionic, cationic, or amphoteric surfactants and mixtures thereof. Theemulsions may also contain additives such as freeze-thaw compositionssuch as polyglycols, representative of which are ethylene glycol,propylene glycol, butylene glycol, mixtures, and copolymers thereof.Other techniques for preparing the emulsions of the present inventionare applicable, for example as shown in U.S. Pat. No. 4,620,878, issuedNov. 4, 1986. The '878 patent also contains details of other suitablesurfactants that may also be employed. Reference can also be made to theemulsion techniques and surfactants contained in U.S. Pat. No.4,501,619, issued Feb. 26, 1985; U.S. Pat. No. 4,631,273, issued Dec.23, 1986; and U.S. Pat. No. 4,842,766, issued June 27, 1989. These fourpatents are considered incorporated herein by reference. It is notedthat the nonionic surfactant of Example IV in an ethoxylatedtrimethylnonanol with an HLB value of 11.7, and is a trademark andproduct of Union Carbide Corporation, Industrial Chemicals Division,Danbury, Conn.

                  TABLE I                                                         ______________________________________                                        Performance of 15% Solids (OSiMeH).sub.0.75 (OSiMeR).sub.0.25                 as Waterproofing Penetrants on Concrete                                               % H.sub.2 O Exclusion                                                 R         1 Day   2 Days     7 Days                                                                              21 Days                                    ______________________________________                                        H         Fail    Fail       Fail  Fail                                       C.sub.6 H.sub.13                                                                        81      73         53    36                                         C.sub.12 H.sub.25                                                                       57      36         Fail  Fail                                       ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        Performance of 30% Solids (OSiMeH).sub.0.75 (OSiMeR).sub.0.25                 as Waterproofing Penetrants on Concrete                                               % H.sub.2 O Exclusion                                                 R         1 Day   2 Days     7 Days                                                                              21 Days                                    ______________________________________                                        H         Fail    Fail       Fail  Fail                                       C.sub.6 H.sub.13                                                                        90      87         77    71                                         C.sub.12 H.sub.25                                                                       85      78         54    27                                         ______________________________________                                    

In the alternate embodiment of the present invention and in thefollowing examples, hydrogen on silicon is replaced with alkoxy byreaction with an alcohol using hydroxylamine catalyst. The reactionproceeds readily and can be controlled by the amount of catalyst used,the preferred level being 0.25 percent based on the weight of siloxane.In this reaction, SiH reacts with hydroxylamine to formO-aminoxysiloxane plus hydrogen. Alcohol reacts with aminoxysiloxane toform alkoxysiloxane plus hydroxylamine. The process repeats until all ofthe SiH is exhausted. The product from this reaction, a low viscosityoil, is a mixture of compounds having an average stoichiometry of(OSiMeOR)₀.75 /(OSiMeC₆ H₁₃)₀.25 where R=Me, Et, or isopropyl. Althoughthis emulsion contains alkoxy on silicon which is hydrolyzable,hydrolysis did not occur after four months of storage. The reason isbelieved to be due to the presence of only one alkoxy group per siliconatom. Emulsions of alkoxysilanes which are less stable have more alkoxygroups per silicone atom than these compositions. In addition, the pH ofthese emulsions is neutral and this contributes towards hydrolyticstability.

EXAMPLE V

The filtered product from Example IV was transferred to a two literround bottom flask equipped with a reflux condenser, a magnetic stirrer,and a heating mantle. 230 grams of absolute ethanol was added to theflask and the mixture was stirred by swirling the flask until a solutionresulted. One gram of N,N-diethylhydrolylamine was added and the flaskwas swirled to mix the amine. Reaction began upon addition of the amineas indicated by significant bubbling. The condenser was placed andstirring was started. Power to the heating mantle was maintained offinitially as heat from the reaction continued to build. About four hourslater, heat from the reaction began to subside and the heating mantlewas turned on to cause a gentle reflux in the flask. Profuse bubblingoccurred six hours into the reaction and stopped after eight hours. Theexcess alcohol was removed using a rotary vacuum evaporator. FTIRanalysis of the product revealed the absence of SiH. To 300 grams ofthis product was added 4 grams of the nonionic surfactant TERGITOL®TMN-6 and 669 grams of distilled water. The mixture was stirred for 30minutes and homogenized using a Gaulin laboratory homogenizer to producean oil in water emulsion having a solids content of about 30 percent byweight. This emulsion was used to treat small 2"×2"×2" concrete blocksand these blocks were tested for water repellency according to ExampleIV.

EXAMPLE VI

A mixture of methylhydrogen cyclosiloxanes, of the formula (OSiMeH)_(n)where n=4,5, and 6, was ethoxylated using ethanol andN,N-diethylhydroxylamine according to the procedure described in ExampleV to produce (OSiMeOEt)_(n) where n=4,5, and 6. The product was a lowviscosity oil and was homogenized with water and surfactant to produce a30 percent solids nonionic emulsion. This material was tested onconcrete blocks using the procedure described above. Table III shows theresults of the tests conducted in Examples V and VI. This alternateembodiment of the present invention is of utility where the evolution ofhydrogen as a by-product is undesirable.

                  TABLE III                                                       ______________________________________                                        Performance of Water-based Masonry Water Repellent*                           on Concrete (OSiMeOEt).sub.0.75 /(OSiMeR).sub.0.25 (30% Solids)               % H.sub.2 O Exclusion                                                         R     1 Day   2 Days  5 Days                                                                              11 Days                                                                              15 Days                                                                              21 Days                             ______________________________________                                        C.sub.6 H.sub.13                                                                    89      85      53    80     78     75                                  OEt   91      95      86    81     73     74                                  ______________________________________                                         *15% (OSiMeH).sub.0.75 /(OSiMeR).sub.0.25 ; 6% TERGITOL ® TMN6; and       79% H.sub.2 O.                                                           

It will be apparent from the foregoing that many other variations andmodifications may be made in the compounds, compositions, structures,and methods described herein without departing substantially from theessential features and concepts of the present invention. Accordingly,it should be clearly understood that the forms of the inventiondescribed herein are exemplary only and are not intended as limitationson the scope of the present invention as defined in the appended claims.

What is claimed is:
 1. A methylalkoxy-methylalkyl cyclosiloxanecopolymer having the formula

    (OSiROR).sub.d (OSiRR').sub.e

where R is an alkyl radical having one to three carbon atoms; R' is thealkyl radical (CH₂)_(c) R; c is an integer having a value of from one toseventeen; d is an integer having a value of from 3 to 10; and e is aninteger having a value of from one to seven.
 2. The copolymer of claim 1in which the integer c has a value of five, six, or seven.
 3. Thecopolymer of claim 1 in which the integer d has a value of three orfour.